Ministry of Higher

Education and
Scientific Research

Advanced Mass Transfer

Master Course

By
Prof. Dr. Ahmed Daham Wiheeb

2020 - 2021
Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

18.5 Diffusion into a falling liquid film (gas absorption)

In this section we present an illustration of forced-convection mass transfer, in which
viscous flow and diffusion occur under such conditions that the velocity field can be
considered virtually unaffected by the diffusion. Specifically, we consider the absorption of
gas A by a laminar falling film of liquid B. The material A is only slightly soluble in B,
so that the viscosity of the liquid is unaffected. We shall make the further restriction that the
diffusion takes place so slowly in the liquid film that A will not "penetrate" very far into the
film-that is, that the penetration distance will be small in comparison with the film thickness.
The system is sketched in Fig. 18.5-1. An example of this kind of system occurs in the
absorption of O2 in H2O.

First, we have to solve the momentum transfer problem to obtain the velocity profile
𝒗𝒛 (𝒙) for the film; this has already been worked out in $2.2 in the absence of mass transfer at
the fluid surface, and we know that the result is:

𝒙 𝟐
𝒗𝒛 (𝒙) = 𝒗𝒎𝒂𝒙 [𝟏 − ( ) ] (18.5 − 1)
𝜹

We note that 𝒄𝑨 will be changing with both 𝒙 and 𝒛. So the element of volume for
the mass balance, we select the volume formed by the intersection of a slab of thickness 𝚫𝒛
with a slab of thickness 𝚫𝒙. Then the mass balance on A over this segment of a film of
width W becomes:

Input – Output = Accumulation

(𝑁𝐴𝑧 )𝑧 . 𝑊Δ𝑥 − (𝑁𝐴𝑧 )𝑧+∆𝑧 . 𝑊Δ𝑥 + (𝑁𝐴𝑥 )𝑥 . 𝑊Δ𝑧 − (𝑁𝐴𝑥 )𝑥+∆𝑥 . 𝑊Δ𝑧 = 0 (18.5 − 2)

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

Dividing Eq. (18.5.1) by (𝑊 ∆𝑥Δ𝑧) and Take the limit: ∆𝑧 → 0 𝑎𝑛𝑑 ∆𝑥 → 0 gives:

𝑑 𝑑
− (𝑁𝐴𝑧 ) − (𝑁 ) = 0
𝑑𝑧 𝑑𝑥 𝐴𝑥
𝑑𝑁𝐴𝑧 𝑑𝑁𝐴𝑥
+ =0 (𝟏𝟖. 𝟓 − 𝟑)
𝑑𝑧 𝑑𝑥
𝑑𝑐𝐴
𝑁𝐴𝑧 = −𝐷𝐴𝐵 + 𝑥𝐴 (𝑁𝐴𝑧 + 𝑁𝐵𝑧 ) ≈ 𝑐𝐴 𝑣𝑧 (𝑥) (𝟏𝟖. 𝟓 − 𝟒)
𝑑𝑧

We neglect the molecular diffusion term in the Eq.(18.5-4), since the transport of A in the
z direction will be primarily by convection.

𝑑𝑐𝐴 𝑑𝑐𝐴
𝑁𝐴𝑥 = −𝐷𝐴𝐵 + 𝑥𝐴 (𝑁𝐴𝑥 + 𝑁𝐵𝑥 ) ≈ −𝐷𝐴𝐵 (𝟏𝟖. 𝟓 − 𝟓)
𝑑𝑥 𝑑𝑥

We neglect the convection term in the Eq.(18.5-5) because in the x direction A moves
predominantly by molecular diffusion, there being almost no convective transport normal to
the wall on account of the very slight solubility of A in B.
Substituting Eq.(18.5-4) and Eq.(18.5-5) into Eq.(18.5-3) gives:

𝑑 𝑑 𝑑𝑐𝐴
(𝑐𝐴 𝑣𝑧 (𝑥)) + (−𝐷𝐴𝐵 )=0 Where: 𝐷𝐴𝐵 is constant
𝑑𝑧 𝑑𝑥 𝑑𝑥

𝑑𝑐𝐴 𝑑 2 𝑐𝐴
𝑣𝑧 (𝑥) = 𝐷𝐴𝐵 (𝟏𝟖. 𝟓 − 𝟔)
𝑑𝑧 𝑑𝑥 2

Substituting Eq.(18.5-1) into Eq.(18.5-6) gives:

𝑥 2 𝑑𝑐𝐴 𝑑2 𝑐𝐴
𝑣𝑚𝑎𝑥 [1 − ( ) ] = 𝐷𝐴𝐵 (𝟏𝟖. 𝟓 − 𝟕)
𝛿 𝑑𝑧 𝑑𝑥 2

Eq.(18.5-7) is to be solved with the following boundary conditions:

𝐵. 𝐶. 1: 𝑎𝑡 𝑧=0 , 𝑐𝐴 = 0 (𝟏𝟖. 𝟓 − 𝟖)

𝐵. 𝐶. 2: 𝑎𝑡 𝑥=0 , 𝑐𝐴 = 𝑐𝐴0 (𝟏𝟖. 𝟓 − 𝟗)

𝜕𝑐𝐴
𝐵. 𝐶. 3: 𝑎𝑡 𝑥=𝛿 , =0 (𝟏𝟖. 𝟓 − 𝟏𝟎)
𝜕𝑥

The first boundary condition corresponds to the fact that the film consists of pure B at the top
(𝑧 = 0), and the second indicates that at the liquid-gas interface the concentration of A is
determined by the solubility of A in B (that is, 𝒄𝑨𝟎 ). The third boundary condition states
that A cannot diffuse through the solid wall.

We seek only a limiting expression valid for "short contact times," that is, for small values of
𝐿
(𝑣 ).
𝑚𝑎𝑥

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

If, as indicated in Fig. 18.5-1, the substance A has penetrated only a short distance into the
film "short contact times", then the species A "has the impression" that the film is moving
throughout with a velocity equal to (𝒗𝒎𝒂𝒙 ). Furthermore if A does not penetrate very far, it
does not "sense" the presence of the solid wall at (𝒙 = 𝜹). Hence, if the film were of infinite
thickness moving with the velocity (𝒗𝒎𝒂𝒙 ), the diffusing material "would not know the
difference." Eq.(18.5-7) becomes:

𝑑𝑐𝐴 𝑑 2 𝑐𝐴
𝑣𝑚𝑎𝑥 = 𝐷𝐴𝐵 (𝟏𝟖. 𝟓 − 𝟏𝟏)
𝑑𝑧 𝑑𝑥 2

And the boundary conditions to solve Eq.(18.5-11) becomes:

𝐵. 𝐶. 1: 𝑎𝑡 𝑧=0 , 𝑐𝐴 = 0 (𝟏𝟖. 𝟓 − 𝟖)

𝐵. 𝐶. 2: 𝑎𝑡 𝑥=0 , 𝑐𝐴 = 𝑐𝐴0 (𝟏𝟖. 𝟓 − 𝟗)

𝐵. 𝐶. 3: 𝑎𝑡 𝑥=∞ , 𝑐𝐴 = 0 (𝟏𝟖. 𝟓 − 𝟏𝟎)

𝑥 𝑥 −
1
𝐿𝑒𝑡: 𝜁 = = 𝑧 2 … … … . . … … (1)
√4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 √4 𝐷𝐴𝐵 ⁄𝑣𝑚𝑎𝑥

𝑥2 𝑥2
→ 𝜁2 = → 𝑧= 2
… … … . . … … (2)
4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 4 𝐷𝐴𝐵 𝜁 ⁄𝑣𝑚𝑎𝑥

2 𝑥2
→ 𝑧 𝜁 = … … … . . … … (3)
4 𝐷𝐴𝐵 ⁄𝑣𝑚𝑎𝑥

2
From Eq.(1) we get: 𝑑𝑥 = 𝑑𝜁 √4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 → 𝑑𝑥 2 = 𝑑 𝜁 (4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 ) … (4)

𝑥2 −2
From Eq. (2)we get: 𝑑𝑧 = × 3 𝑑𝜁
4 𝐷𝐴𝐵 ⁄𝑣𝑚𝑎𝑥 𝜁
2
𝑥 2
From Eq. (3) we get: = 𝑧 𝜁
4 𝐷𝐴𝐵 ⁄𝑣𝑚𝑎𝑥
2 −2 𝑧
Then: 𝑑𝑧 = 𝑧 𝜁 × 3 𝑑𝜁 → 𝑑𝑧 = −2 𝑑𝜁 … … . . … … (5)
𝜁 𝜁

Substituting Eq.(4) and Eq.(5) into Eq.(18.5-11) gives:

𝑑𝑐𝐴 𝑑2 𝑐𝐴
𝑣𝑚𝑎𝑥 = 𝐷𝐴𝐵 2
𝑧 𝑑𝜁 (4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 )
(−2 ) 𝑑𝜁
𝜁

𝑑𝑐𝐴 𝑑2 𝑐𝐴
−2 𝜁 =
𝑑𝜁 𝑑𝜁
2

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝑑 2 𝑐𝐴 𝑑𝑐𝐴
+ 2 𝜁 =0
𝑑𝜁
2 𝑑𝜁

𝑑𝑐𝐴 𝑑𝑝 𝑑2 𝑐𝐴
𝐿𝑒𝑡: 𝑝= → =
𝑑𝜁 𝑑𝜁 𝑑𝜁
2

𝑑𝑝 𝑑𝑝
+2𝜁𝑝 =0 → = −2𝜁 𝑑𝜁
𝑑𝜁 𝑝

2 2
ln 𝑝 = −𝜁 + ln 𝐶1 → 𝑝 = 𝐶1 𝑒 −𝜁

𝑑𝑐𝐴 2 2 √𝜋 2
= 𝐶1 𝑒 −𝜁 → 𝑑𝑐𝐴 = 𝐶1 𝑒 −𝜁 𝑑𝜁 × ×
𝑑𝜁 2 √𝜋
𝜁
𝐶1 √𝜋 2 −𝜁2
𝑐𝐴 = ∫ 𝑒 𝑑𝜁
2 √𝜋
0
𝑥
2 2
𝑤ℎ𝑒𝑟𝑒: erf(𝑥) = ∫ 𝑒 −𝑧 𝑑𝑧
√𝜋
0

→ 𝒄𝑨 = 𝑪𝟑 𝐞𝐫𝐟(𝜻) + 𝑪𝟐 … … … … … (∗)

𝐶1 √𝜋
𝑤ℎ𝑒𝑟𝑒: 𝐶3 =
2

And the boundary conditions to solve Eq.(*) becomes:

𝐵. 𝐶. 1: 𝑎𝑡 𝑧=0 → 𝜁=∞, 𝑐𝐴 = 0

𝐵. 𝐶. 2: 𝑎𝑡 𝑥=0 → 𝜁=0 , 𝑐𝐴 = 𝑐𝐴0

𝐵. 𝐶. 3: 𝑎𝑡 𝑥=∞ → 𝜁=∞ , 𝑐𝐴 = 0

Applying B.C.1 and B.C.2:

0 = 𝐶3 erf(∞) + 𝐶2 → 𝐶3 = −𝐶2 , 𝑤ℎ𝑒𝑟𝑒: erf(∞) = 1

𝑐𝐴0 = 𝐶3 erf(0) + 𝐶2 → 𝑪𝟐 = 𝒄𝑨𝟎 , 𝑤ℎ𝑒𝑟𝑒: erf(0) = 0

→ 𝑪𝟑 = −𝒄𝑨𝟎

Substituting the values of C2 and C3 into Eq.(*) gives:

𝑐𝐴
𝑐𝐴 = −𝑐𝐴0 erf(𝜁) + 𝑐𝐴0 → = 1 − 𝑒𝑟𝑓(𝜁)
𝑐𝐴0

𝑐𝐴 𝑥
→ = 1 − erf ( )
𝑐𝐴0 √4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝒄𝑨 𝒙
∴ = 𝐞𝐫𝐟𝐜 ( ) (𝟏𝟖. 𝟓 − 𝟏𝟔)
𝒄𝑨𝟎 √𝟒 𝑫𝑨𝑩 𝒛⁄𝒗𝒎𝒂𝒙

𝑊ℎ𝑒𝑟𝑒: 1 − erf(𝑥) = erf c(𝑥) complementary error function

Once the concentration profiles are known, the local mass flux at the gas-liquid interface may
be found as follows:

𝑑𝑐𝐴
(𝑁𝐴𝑥 )𝑥=0 = −𝐷𝐴𝐵 ( )
𝑑𝑥 𝑥=0

𝑑𝑐𝐴 𝑑𝑐𝐴 𝑑𝜁
→ =
𝑑𝑥 𝑑𝜁 𝑑𝑥

𝒅 𝟐 −𝒙𝟐
𝒘𝒉𝒆𝒓𝒆: 𝐞𝐫𝐟(𝒙) = 𝒆
𝒅𝒙 √𝝅

𝑑𝑐𝐴 2 𝐶3 −𝜁2 2 −𝜁 2
From Eq. (∗) → = 𝑒 = (−𝑐𝐴0 ) 𝑒
𝑑𝜁 √𝜋 √𝜋

𝑑𝜁 1
𝐹𝑟𝑜𝑚 𝐸𝑞. (4) 𝑤𝑒 𝑔𝑒𝑡: =
𝑑𝑥 √4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥

𝑑𝑐𝐴 2 −𝜁 2 1
𝑇ℎ𝑒𝑛 → = [(−𝑐𝐴0 ) 𝑒 ] [ ]
𝑑𝑥 √𝜋 √4 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥

2
𝑑𝑐𝐴 −𝑐𝐴0 𝑒 −𝜁
→ =
𝑑𝑥 √𝜋 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥

2
−𝑐𝐴0 𝑒 −𝜁
(𝑁𝐴𝑥 )𝑥=0 = −𝐷𝐴𝐵 ( )
√𝜋 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥 𝑥=0

𝑐𝐴0 2
(𝑁𝐴𝑥 )𝑥=0 = 𝐷𝐴𝐵 ( ) , 𝑎𝑡 𝑥 = 0 → 𝜁 = 0 → 𝑒 −𝜁 = 𝑒 0 = 1
√𝜋 𝐷𝐴𝐵 𝑧⁄𝑣𝑚𝑎𝑥

𝐷𝐴𝐵 𝑣𝑚𝑎𝑥
(𝑁𝐴𝑥 )𝑥=0 = 𝑐𝐴0 √ (𝟏𝟖. 𝟓 − 𝟏𝟕)
𝜋𝑧

Then the total molar flow of A across the surface at 𝒙 = 𝟎 (i.e., being absorbed by a liquid
film of length L and width W) is:

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝑊 𝐿

𝑊𝐴 = ∫ ∫(𝑁𝐴𝑥 )𝑥=0 𝑑𝑧 𝑑𝑦
0 0

𝐿
𝐷𝐴𝐵 𝑣𝑚𝑎𝑥 1
𝑊𝐴 = 𝑊 𝑐𝐴0 √ ∫ 𝑑𝑧
𝜋 √𝑧
0

1 𝐿
𝐷𝐴𝐵 𝑣𝑚𝑎𝑥 𝑧 2
𝑊𝐴 = 𝑊 𝑐𝐴0 √ ( )
𝜋 1
2 0

4 𝐷𝐴𝐵 𝑣𝑚𝑎𝑥 𝐿 4 𝐷𝐴𝐵 𝑣𝑚𝑎𝑥

𝑊𝐴 = 𝑊 𝑐𝐴0 √ = 𝑊 𝐿 𝑐𝐴0 √ (𝟏𝟖. 𝟓 − 𝟏𝟖)
𝜋 𝜋𝐿

18.7 Diffusion and chemical reaction inside a porous catalyst

Up to this point we have discussed diffusion in gases and liquids in systems of simple
geometry. We now wish to apply the shell mass balance method and Fick's first law to
describe diffusion within a porous catalyst pellet. We consider a spherical porous catalyst
particle of radius R, as shown in Fig. 18.7-1. This particle is in a catalytic reactor, where it is
submerged in a gas stream containing the reactant A and the product B. Species A diffuses
through the tortuous passages in the catalyst and is converted to B on the catalytic surfaces,
as sketched in Fig. 18.7-2.

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

We start by making a mass balance for species A on a spherical shell of thickness (∆𝒓) within
a single catalyst particle:

Input – Output + Generation = Accumulation

(𝑁𝐴𝑟 )𝑟 . 4𝜋𝑟 2 − (𝑁𝐴𝑟 )𝑟+∆𝑟 .4𝜋(𝑟 + ∆𝑟)2 + 𝑅𝐴 . 4𝜋𝑟 2 ∆𝑟 = 0 (𝟏𝟖. 𝟕 − 𝟏)

Where:
(𝑁𝐴𝑟 )𝑟 ∶ is the number of moles of A passing in the r direction through an imaginary
spherical surface at a distance r from the center of the sphere (input).

(𝑁𝐴𝑟 )𝑟+∆𝑟 ∶ is the number of moles of A passing in the r direction through an imaginary
spherical surface at a distance 𝒓 + ∆𝒓 from the center of the sphere (output).

𝑅𝐴 . 4𝜋𝑟 2 ∆𝑟 ∶ is the molar rate of production of A by chemical reaction in the shell of

thickness ∆𝒓 (generation).

Dividing Eq.(18.7-1) by 𝟒𝝅∆𝒓 and letting ∆𝒓 → 𝟎 gives:

(𝑟 2 𝑁𝐴𝑟 )𝑟+∆𝑟 − (𝑟 2 𝑁𝐴𝑟 )𝑟

lim = 𝑟 2 𝑅𝐴 (𝟏𝟖. 𝟕 − 𝟐)
∆𝒓→𝟎 ∆𝑟

or, using the definition of the first derivative,

𝑑 2
(𝑟 𝑁𝐴𝑟 ) = 𝑟 2 𝑅𝐴 (𝟏𝟖. 𝟕 − 𝟑)
𝑑𝑟

We now define an "effective diffusivity" for species A in the porous medium by:

𝑑𝑐𝐴
𝑁𝐴𝑟 = − 𝐷𝐴 (𝟏𝟖. 𝟕 − 𝟒)
𝑑𝑟
Where:

𝑐𝐴 ∶ is the concentration of the gas A contained within the pores.

The effective diffusivity 𝑫𝑨 must be measured experimentally. It depends generally on

pressure and temperature and also on the catalyst pore structure. The actual mechanism for
diffusion in pores is complex, since the pore dimensions may be smaller than the mean free
path of the diffusing molecules. We do not belabor the question of mechanism here but
assume only that Eq. 18.7-4 can adequately represent the diffusion process.

Substituting Eq.(18.7-4) into Eq.(18.7-3) gives:

1 𝑑 𝑑𝑐𝐴
𝐷𝐴 2
( 𝑟2 ) = −𝑅𝐴 (𝟏𝟖. 𝟕 − 𝟓)
𝑟 𝑑𝑟 𝑑𝑟

For first order reaction: 𝑅𝐴 = −𝑘1′′ 𝑎𝑐𝐴

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

Where:

𝑎 ∶ is the available catalytic surface per unit volume.

Eq.(18.7-5) becomes:

1 𝑑 𝑑𝑐𝐴
𝐷𝐴 2
( 𝑟2 ) = 𝑘1′′ 𝑎𝑐𝐴 (𝟏𝟖. 𝟕 − 𝟔)
𝑟 𝑑𝑟 𝑑𝑟
𝑑 𝑑𝑐𝐴 𝑘1′′ 𝑎𝑐𝐴
( 𝑟2 ) − 𝑟2 =0
𝑑𝑟 𝑑𝑟 𝐷𝐴

𝑑 2 𝑐𝐴 𝑑𝑐𝐴 𝑘 ′′ 𝑎𝑐𝐴
2 1
𝑟2 + 2𝑟 − 𝑟 =0 (1)
𝑑𝑟 2 𝑑𝑟 𝐷𝐴

Changing the variables of Eq.(18.7-6) as below:

𝑢
𝐿𝑒𝑡: 𝑐𝐴 = (2)
𝑟
𝑑𝑐𝐴 1 𝑑𝑢 𝑢
= − 2 (3)
𝑑𝑟 𝑟 𝑑𝑟 𝑟
𝑑 2 𝑐𝐴 1 𝑑2 𝑢 1 𝑑𝑢 1 𝑑𝑢 2𝑢
= − − + 3
𝑑𝑟 2 𝑟 𝑑𝑟 2 𝑟 2 𝑑𝑟 𝑟 2 𝑑𝑟 𝑟
𝑑 2 𝑐𝐴 1 𝑑2 𝑢 2 𝑑𝑢 2𝑢
= − + 3 (4)
𝑑𝑟 2 𝑟 𝑑𝑟 2 𝑟 2 𝑑𝑟 𝑟

Substituting Eq. (3) and (4) into Eq.(1) gives:

2
1 𝑑2𝑢 2 𝑑𝑢 2𝑢 1 𝑑𝑢 𝑢 𝑘 ′′ 𝑎𝑐𝐴
2 1
𝑟 ( − + 3 ) + 2𝑟 ( − )− 𝑟 =0 ÷𝑟
𝑟 𝑑𝑟 2 𝑟 2 𝑑𝑟 𝑟 𝑟 𝑑𝑟 𝑟 2 𝐷𝐴

𝑑 2 𝑢 2 𝑑𝑢 2𝑢 2 𝑑𝑢 2𝑢 𝑘1′′ 𝑎𝑐𝐴
− + 2+ − 2− 𝑟 =0
𝑑𝑟 2 𝑟 𝑑𝑟 𝑟 𝑟 𝑑𝑟 𝑟 𝐷𝐴

𝑑2𝑢 𝑘1′′ 𝑎𝑐𝐴

− 𝑟 =0 𝑤ℎ𝑒𝑟𝑒: 𝑐𝐴 𝑟 = 𝑢
𝑑𝑟 2 𝐷𝐴

𝑑2𝑢 𝑘1′′ 𝑎 𝑘1′′ 𝑎

2
𝑘1′′ 𝑎
2
− 𝑢=0 → (𝐷 − ) 𝑢=0 → 𝑚 − =0
𝑑𝑟 2 𝐷𝐴 𝐷𝐴 𝐷𝐴

𝑘1′′ 𝑎
𝑚 =±√
𝐷𝐴

The solution becomes:

𝑘 ′′ 𝑎 𝑘 ′′ 𝑎 𝑘 ′′ 𝑎 𝑘 ′′ 𝑎
√ 1 𝑟 −√ 1 𝑟 √ 1 𝑟 −√ 1 𝑟
𝐷𝐴 𝐷𝐴 𝐷𝐴 𝐷𝐴
𝑢 = 𝐶1 𝑒 + 𝐶2 𝑒 → 𝑐𝐴 𝑟 = 𝐶1 𝑒 + 𝐶2 𝑒

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝑘1′′ 𝑎 𝑘1′′ 𝑎
𝐶1 √ 𝐷𝐴
𝑟 𝐶2 −√ 𝐷𝐴
𝑟
𝑐𝐴 = 𝑒 + 𝑒 (6)
𝑟 𝑟

And the boundary conditions to solve Eq. (6) becomes:

𝐵. 𝐶. 1: 𝑎𝑡 𝑟=𝑅 , 𝑐𝐴 = 𝑐𝐴𝑅
𝐵. 𝐶. 2: 𝑎𝑡 𝑟=0 , 𝑐𝐴 = finite

Applying B.C.1 and B.C.2:

𝑘 ′′ 𝑎 𝑘 ′′ 𝑎
√ 1 (0) −√ 1 (0)
𝐷𝐴 𝐷𝐴
𝑐𝐴 . (0) = 𝐶1 𝑒 + 𝐶1 𝑒 → 𝐶1 + 𝐶2 = 0 → 𝑪𝟏 = −𝑪𝟐

𝑘1′′ 𝑎 𝑘1′′ 𝑎
𝐶1 √ 𝐷𝐴
𝑅 𝐶2 −√ 𝐷𝐴
𝑅 𝑹 𝒄𝑨𝑹
𝑐𝐴𝑅 = 𝑒 + 𝑒 → 𝑪𝟏 =
𝑅 𝑅 𝒌′′ 𝒂 𝒌′′ 𝒂
√ 𝟏 𝑹 −√ 𝟏 𝑹
𝑫𝑨 𝑫𝑨
𝒆 −𝒆
− 𝑹 𝒄𝑨𝑹
→ 𝑪𝟐 =
𝒌′′ 𝒂 𝒌′′ 𝒂
√ 𝟏 𝑹 −√ 𝟏 𝑹
𝑫𝑨 𝑫𝑨
𝒆 −𝒆

Substituting the values of 𝑪𝟏 and 𝑪𝟐 into Eq.(6) gives:

𝑘 ′′ 𝑎 𝑘 ′′ 𝑎
𝑐𝐴 𝑅 1 √ 1 𝑟 −√ 1 𝑟
𝐷𝐴 𝐷𝐴
= [𝑒 − 𝑒 ]
𝑐𝐴𝑅 𝑟 𝑘 ′′ 𝑎 𝑘 ′′ 𝑎
√ 1 𝑅 −√ 1 𝑅
𝐷𝐴 𝐷𝐴
𝑒 −𝑒

𝑘1′′ 𝑎
sinh √
𝑐𝐴 𝑅 𝐷𝐴 𝑟
= (𝟏𝟖. 𝟕 − 𝟗)
𝑐𝐴𝑅 𝑟 𝑘1′′ 𝑎
sinh √ 𝐷 𝑅
𝐴

In studies on chemical kinetics and catalysis one is frequently interested in the molar flux
𝑵𝑨𝑹 or the molar flow 𝑾𝑨𝑹 at the surface 𝒓 = 𝑹:

𝑑𝑐𝐴
𝑊𝐴𝑅 = 4𝜋𝑅 2 𝑁𝐴𝑅 = −4𝜋𝑅 2 𝐷𝐴 ( ) (𝟏𝟖. 𝟕 − 𝟏𝟎)
𝑑𝑟 𝑟=𝑅

𝑘1′′ 𝑎
𝑑𝑐𝐴 𝑅 𝑐𝐴𝑅 1 𝑘1′′ 𝑎 𝑘1′′ 𝑎 sinh √ 𝐷 𝑟
𝐴
𝑊ℎ𝑒𝑟𝑒: = √ cosh √ 𝑟−
𝑑𝑟 𝑘 ′′ 𝑎 𝑟 𝐷𝐴 𝐷𝐴 𝑟2
sinh √ 1 𝑅
𝐷𝐴 [ ]

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝑘1′′ 𝑎
𝑑𝑐𝐴 𝑘1′′ 𝑎 cosh √ 𝑅 1
𝐷𝐴
( ) = √ − 𝑐𝐴𝑅
𝑑𝑟 𝑟=𝑅 𝐷𝐴 𝑘1′′ 𝑎 𝑅
sinh √ 𝐷 𝑅
[ 𝐴 ]

𝑑𝑐𝐴 𝑘1′′ 𝑎 𝑘1′′ 𝑎 1

( ) = [√ coth (√ 𝑅) − ] 𝑐𝐴𝑅
𝑑𝑟 𝑟=𝑅 𝐷𝐴 𝐷𝐴 𝑅

𝑘1′′ 𝑎 𝑘1′′ 𝑎 1
𝑊𝐴𝑅 = −4𝜋𝑅 2 𝐷𝐴 [ √ coth (√ 𝑅) − ] 𝑐𝐴𝑅
𝐷𝐴 𝐷𝐴 𝑅

𝑘1′′ 𝑎 𝑘1′′ 𝑎
𝑊𝐴𝑅 = 4𝜋𝑅 𝐷𝐴 𝑐𝐴𝑅 [1 − √ 𝑅 coth (√ 𝑅)] (𝟏𝟖. 𝟕 − 𝟏𝟏)
𝐷𝐴 𝐷𝐴

This result gives the rate of conversion (in moles/sec) of A to B in a single catalyst particle
of radius R in terms of the parameters describing the diffusion and reaction processes.

If the catalytically active surface were all exposed to the stream of concentration 𝒄𝑨𝑹
(surface is too active) then the species A would not have to diffuse through the pores to a
reaction site. The molar rate of conversion in this case is:

4
𝑊𝐴𝑅,0 = ( 𝜋 𝑅 3 ) (𝑎) (−𝑘1′′ 𝑐𝐴𝑅 ) (𝟏𝟖. 𝟕 − 𝟏𝟐)
3

4
𝑊𝐴𝑅,0 = − 𝜋 𝑅 3 𝑎 𝑘1′′ 𝑐𝐴𝑅
3

Dividing Eq.(18.7-12) by Eq.(18.7-11) gives:

𝑊𝐴𝑅 3
𝜂𝐴 = = 2 (∅ coth ∅ − 1) (𝟏𝟖. 𝟕 − 𝟏𝟑)
𝑊𝐴𝑅,0 ∅

Where:

𝑘1′′ 𝑎
∅= √ 𝑅 = 𝑖𝑠 𝑡ℎ𝑒 𝑇ℎ𝑖𝑒𝑙𝑒 𝑚𝑜𝑑𝑢𝑙𝑢𝑠
𝐷𝐴
𝜂𝐴 = 𝑖𝑠 𝑡ℎ𝑒 𝑒𝑓𝑒𝑐𝑡𝑖𝑣𝑒𝑛𝑒𝑠𝑠 𝑓𝑎𝑐𝑡𝑜𝑟

11
Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

18.8 Diffusion in a three-component gas system

Up to this point the systems we have discussed have been binary systems. To illustrate
the setting up of multi-component diffusion problems for gases, we rework the initial
evaporation problem of $18.2 when liquid water (species 1) is evaporating into air, regarded
as a binary mixture of nitrogen (2) and oxygen (3) at 1 atm and 352 K.

• We take the air-water interface to be at 𝒛 = 𝟎 and the top end of the diffusion tube to
be at 𝒛 = 𝑳.

• We consider the vapor pressure of water to be known, so that 𝒙𝟏 is known:

341
𝒂𝒕 𝒛=𝟎 , 𝒙𝟏𝟎 = = 0.449
760
• The mole fractions of all three gases are known as:

𝒂𝒕 𝒛=𝑳 , 𝒙𝟏𝑳 = 0.1

𝒙𝟐𝑳 = 0.75
𝒙𝟑𝑳 = 0.15

• The diffusion tube has a length of 𝑳 = 𝟏𝟏. 𝟐 𝒄𝒎

The conservation of mass leads to the following expressions:

𝑑𝑁𝛼𝑧
=0 , 𝑤ℎ𝑒𝑟𝑒: 𝛼 = 1, 2, 3, … .. (𝟏𝟖. 𝟖 − 𝟏)
𝑑𝑧
From this it may be concluded that the molar fluxes of the three species are all constants at
steady state. Since species 2 and 3 are not moving (stagnant), we conclude that:

𝑁2𝑧 = 0 𝑎𝑛𝑑 𝑁3𝑧 = 0

𝑎𝑛𝑑 ∶ 𝑥1 + 𝑥2 + 𝑥3 = 1

Diffusion of species 1 into the mixture:

𝑑𝑥1
𝑁1𝑧 = −𝑐 𝐷12 + 𝑥1 (𝑁1𝑧 + 𝑁2𝑧 + 𝑁3𝑧 )
𝑑𝑧
−𝑐 𝐷12 𝑑𝑥1
→ 𝑁1𝑧 =
1 − 𝑥1 𝑑𝑧

Diffusion of species 2 into the mixture:

𝑑𝑥2
𝑁2𝑧 = −𝑐 𝐷12 + 𝑥2 (𝑁1𝑧 + 𝑁2𝑧 + 𝑁3𝑧 )
𝑑𝑧
𝑑𝑥2 𝒅𝒙𝟐 𝑵𝟏𝒛
→ 𝑁1𝑧 𝑥2 = 𝑐 𝐷12 → = 𝒙 (𝟏𝟖. 𝟖 − 𝟐)
𝑑𝑧 𝒅𝒛 𝒄 𝑫𝟏𝟐 𝟐

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

Diffusion of species 3 into the mixture:

𝑑𝑥3
𝑁3𝑧 = −𝑐 𝐷13 + 𝑥3 (𝑁1𝑧 + 𝑁2𝑧 + 𝑁3𝑧 )
𝑑𝑧
𝑑𝑥3 𝒅𝒙𝟑 𝑵𝟏𝒛
→ 𝑁1𝑧 𝑥3 = 𝑐 𝐷13 → = 𝒙 (𝟏𝟖. 𝟖 − 𝟑)
𝑑𝑧 𝒅𝒛 𝒄 𝑫𝟏𝟑 𝟑

These equations can be integrated from an arbitrary height 𝒛 to the top of the tube at L
, to give for constant 𝑐𝐷𝐴𝐵 :
𝑥2𝐿 𝐿
𝑑𝑥2 𝑁1𝑧
∫ = ∫ 𝑑𝑧 (𝟏𝟖. 𝟖 − 𝟒)
𝑥2 𝑐 𝐷12
𝑥2 𝑧

𝑥3𝐿 𝐿
𝑑𝑥3 𝑁1𝑧
𝑎𝑛𝑑 ∫ = ∫ 𝑑𝑧 (𝟏𝟖. 𝟖 − 𝟓)
𝑥3 𝑐 𝐷13
𝑥3 𝑧

Integration Eq.(18.8-4) gives:

𝑥2 𝑁1𝑧 𝑥2 𝑁1𝑧 (𝐿 − 𝑧)
ln =− (𝐿 − 𝑧) → = 𝑒𝑥𝑝 (− ) (𝟏𝟖. 𝟖 − 𝟔)
𝑥2𝐿 𝑐 𝐷12 𝑥2𝐿 𝑐 𝐷12

Integration Eq.(18.8-5) gives:

𝑥3 𝑁1𝑧 𝑥3 𝑁1𝑧 (𝐿 − 𝑧)
ln =− (𝐿 − 𝑧) → = 𝑒𝑥𝑝 (− ) (𝟏𝟖. 𝟖 − 𝟕)
𝑥3𝐿 𝑐 𝐷13 𝑥3𝐿 𝑐 𝐷13

𝑤ℎ𝑒𝑟𝑒 ∶ 𝑥1 = 1 − 𝑥2 − 𝑥3

Then the mole fraction profile of water vapor (𝑥1 ) in the diffusion column will be:

𝑁1𝑧 (𝐿 − 𝑧) 𝑁1𝑧 (𝐿 − 𝑧)
𝑥1 = 1 − 𝑥2𝐿 𝑒𝑥𝑝 (− ) − 𝑥3𝐿 𝑒𝑥𝑝 (− ) (𝟏𝟖. 𝟖 − 𝟖)
𝑐 𝐷12 𝑐 𝐷13

When we apply the boundary condition:

𝒂𝒕 𝒛=𝟎 , 𝒙𝟏 = 𝒙𝟏𝟎

𝑁1𝑧 𝐿 𝑁1𝑧 𝐿
𝑥10 = 1 − 𝑥2𝐿 𝑒𝑥𝑝 (− ) − 𝑥3𝐿 𝑒𝑥𝑝 (− ) (𝟏𝟖. 𝟖 − 𝟗)
𝑐 𝐷12 𝑐 𝐷13

Where:

𝐷12 = 0.364 𝑐𝑚2 ⁄𝑠 𝑎𝑛𝑑 𝐷13 = 0.357 𝑐𝑚2 ⁄𝑠 𝑎𝑡 1 𝑎𝑡𝑚 𝑎𝑛𝑑 352K

𝑐 = 3.46 × 10−5 𝑔𝑚⁄𝑐𝑚3

341
𝒙𝟏𝟎 = = 0.449
760

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Advanced Mass Transfer Master Course Prof. Dr. Ahmed Daham

𝑥1𝐿 = 0.1 , 𝑥2𝐿 = 0.75 , 𝑥3𝐿 = 0.15 𝑎𝑛𝑑 𝐿 = 11.2 𝑐𝑚

𝑁1𝑧 (11.2)
0.449 = 1 − (0.75 + 0.15) 𝑒𝑥𝑝 (− )
(3.46 × 10−5 )(0.36)

𝑁1𝑧 = 5.523 × 10−7 𝑔𝑚⁄𝑐𝑚2 . 𝑠

14